Kinetic theory of chemical reactions in dense fluids

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Abstract:

A kinetic theory description of a dense chemically reacting fluid is presented. The kinetic equation takes into account the effects of correlated binary collision events and involves the "repeated ring" operator. Expressions for the rate coefficient are derived from the kinetic equation by means of projection operator techniques. The resulting expressions for the rate coefficient incorporate several features. They show how the dynamics of the reactive collision events lead to a coupling to the diffusive modes of the fluid. The rate coefficient expression is valid in the limit where binary dynamics dominate as well as in the diffusion controlled limit where collective solvent effects play an important role. The frequency and time dependence of the rate kernels and rate coeffiicients are also calculated. The manner in which the kinetic theory can be used to take into account the contributions to the rate coefficient which are higher order in the concentration is described and the relation to other theories is discussed. © 1978 American Institute of Physics.